Process for breaking petroleum emulsions



tented Jy 18, 1944 2,353,699 PRQCESS FOR BREAKING- PETROLEUM EIONSMelvin De Groote, University Qity, and Bed Keiser, Webster Groves, Mo,assignors to lPetrolite Corporation, Ltd, Wilmington, Del, a

corporation of Delaware No revails. Application .Fune 15, 1942,

Serial No. 447,156

% P out This invention relates primarily tothe resolution of petroleumemulsions.

The main object of our invention is to provide a novel process forresolving petroleum emulsions of the water-in-oil type, that arecommonly referred to as "cut oil, roil oil," emulsified oil, etc., andwhich comprise fine droplets of natwally-occurring waters or brinesdispersed in a more'or less permanent state throughout the oil whichconstitutes the continuous phase of the emulsion. Another object is toprovide an economical and rapid process for separating emulsions whichhave been prepared under controlled conditions from mineral oil, such ascrude petroleum and relatively soft waters or weak brines. Controlledemulsification and subsequent demulsiflcation under the conditions justmentioned is of significant value in removing impurities, particularlyinorganlc salts, from pipeline oil.

We have discovered that it one oxyallzylates glycerol so as to introduceat least three oiryalliylene radicals for each hydroryl group, and ifthe product so obtained is reacted with a polybasic carboiry acid havingnot over eight carbon atoms, and in such a manner as to yield afractional ester, due to the presence of at least one free carbonylradical, one can then esteriiy said acidic material or intermediateproduct with at least one mole of an alcoholic compound of the typeherein described to give a variety of new compositions of matter whichare emclent demulsifiers for crude oil emulsions.

The compounds used as the demulsifier in our herein described processmay be produced in any suitable manner, but are usually manufactured byfollowing one of two general procedures. In one of said procedures theoxyalkylated glycerol, which is, in essence, a polyhydrlc alcohol, isreacted with a polybasic acid so as to give an acidic material orintermediate product, which, in turn, is reacted with an alcoholic bodyof the kind hereinafter described, and momentarily indicated by theformula Rl(H)m. Genetically, the alcoholic body herein contemplated maybe considered a member of the class in which m may vary from 1 to 10,although the specific significance of m in the present instance will behereinafter indicated. The second procedure is to react an alcohol ofthe formula type R1(OH)1n with a polybasic acid so as to produce anintermediate product, and then react said intermediate product orfractional ester with the selected oxyalkylated glycerol.

Glycerol may be conveniently indicated by the following formula:

/0H CaHsOH If treated with an oxyalkylatinn agent, and momentarilyconsideration will be limited to an oxyethylating agent, one may obtainan oxyethylated lycerol oi the following formula type:

(C:Hl0)n'1 1 c,H.orc,n.0)..-n

(CIH40)||'H in which the value of u may vary from 3 to 10 and all thevalues of n need not be identical.

If a polybaslc carboxy acid be indicated by the formula:

coon

R-COOH COOH then the acyclic reaction product of one mole ofoxyethylated glycerol and one mole of a polybasic carboxy acid may beindicated by the following formula:

(cimomoocmooomw C3H5OS-(CIHOLVH (CzHiOLvH in which n" has the value ofone or two. Similarly, if two moles of the polybasic acid be used, thenthe compound may be indicated by the following formula:

(ciniou ooomcoomfl (jsHsOs-(UzHiOLuOOCRGZQOHM" (CaHlOLuH Likewise, ifthree moles of a polybasic acid are employed, the compound may beindicated by the following formula:

(CiHlOLe'OOGRfllOOHL CIH503"(C2HO)MOOCR(CO0H)n" (oimowooomoooms- If afractional ester of the kind exemplified by the three preceding formulasis reacted with one or more moles of an alcohol of the kind previouslydescribed in a generic sense as R1(OH)m, thenobviously, one may obtaina. material of the type indicated by the following formula:

in which :1: is 0, 1, or 2, y is 0, 1, or 2, andz is 1, 2, or 3, and :c'is 0 or 1, and y is 1 or 2.

It has been previously stated that compounds of the type hereincontemplated may be obtained by oxyalkylating agents, without beinglimited to ethylene oxide. Suitable oxyalkylating agents includeethylene oxide, propylene oxide, butylene oxide and glycid, which,although not included, strictly speaking, by the unitary structurecflrnno, is included within the meaning of the hereto appended claimsand may be simply considered as a variant of proplene oxide, i. e.,hydroxypropylene oxide. Similarly, where a carboxylic hydrogen atomappears, it may be replaced by metal, an ammonium radical, orsubstituted ammonium radical, or by an organic group derived from analcohol, such as an aliphatic alcohol, an aralkyl alcohol, or analicyclic alcohol. It may also be converted into an amide, including apolyaminoamide. Thus, the perceding formula may be rewritten in itsbroader scope, as follows:

[(cmnmfl'oocmc002m].

tion steps. As is well known, esteriflcation procedures can be carriedout in various manners,

but generally speaking, esteriilcations can be car-.

ried out at the lowestv feasible temperatures by using one of severalprocedures. One procedure is to pass an inert dried gas through the massto be esterified, and have present at the same time a small amount of acatalyst, such as dried HCl gas, a dried sulfonic acid, or the like.Another and better procedure, in many instances, is

to employ the vapors of a suitable liquid, so as to remove any waterformed and condense both the vapors of the liquid employed and the waterin such a manner as to trap out the water and re-v turn the liquid tothe reacting vessel. This procedure is commonly employed in the arts,and for convenience, reference is made to U. S. Patent No. 2,264,759,dated December 2, 1941, to Paul C. Jones.

Referring again to the last two formulas indicating the compounds underconsideration, it can be readily understood that such compounds, innumei ous instances, have th property of polyfuncti'onality. In view ofthis fact, where there is at least one residual carboxyl and at leastone residual hydroxyl, one would expect that under suitable conditions,instead of obtaining the monomericcompounds indicated, one would inreality obtain a polymerin the sense, for example, that polyethyleneglycols'represent a polymer of ethylene glycol. The 1 term-"polymer" isfrequently used to indicate the polymerized product derived from amonomer. in which the polymer has the same identical composition as themonomer. In the present instance, however, polymerization involves thesplitting and loss of water so that the process is essentiallyself-esteriflcation. Thus, strictly speaking, the polymeric compoundsare not absolutely'pelymers of the monomeric comassaeeo in the appendedclaims to polymers is intended to include the self-esterificationproducts of the monomeric compounds.

In view ,of what has been said, and in view of the recognized hydrophileproperties of the recurring oxyalkylene linkages, particularly theoxyethylene linkage, it-is apparent that the materials hereincontemplated may vary from compounds which are clearly water-solublethrough self-emulsifying oils, to materials which are balsam-like and.sub-resinous or semi-resinous in nature. The compounds may vary frommonomers to polymers, in which the unitary structure appears a number oftimes, for instance, 10 or 12' times. It is to be noted that trueresins, i. e., truly insoluble materials of a hard plastic nature, arenot herein included. In other words,

the polymerized compounds are soluble to a fairly definite extent, forinstance, at least 5% in some solvents, such as water, alcohol, benzene,dichloroethyl ether, acetone, cresylic. acid, acetic acid, ethylacetate, dioxane, or the like. This is simply another way of statingthat the polymerized product contemplated must be of the sub-resinoustype, which is commonly referred to as an A resin, or a B resin, asdistinguished from a C resin,

which is a highly infusible, insoluble resin -(see Ellis, Chemistry ofSynthetic Resins (1935) p ges 86 et seq). I

Reviewing the form as presented, it is obvious that one may obtaincompounds within the scope disclosed, which contain neither a freehydroxyl nor a free carboxyl group, and one may also obtain a compoundof the type in which there is present at least one free carboxyl, or atleast,

one free hydroxyl, or both. The word polar has sometimes been used inthe arts in this particular sense to indicate the presence of at leastone free hydroxyl group, or at least one free carboxyl. group, or both.In the case of the free carboxyl group, the carboxylic hydrogen atommay, of course, be replaced by any i'onizable hydrogen atom equivalent,such, for example, as a metal, an ammonium radical, a substitutedammonium radical, etc. In the hereto appended claims the word polar isused in this specific sense.

We are aware that compounds similar to thosecontemplated in the presentinstance may be derived from lpolyhydroxylated compounds having morethan three hydroxyl groups. For instance,

they may be derived from acyclic diglycerol,"triglycerol, tetraglycerol,mixed polyglyce'rols, mannitol. sorbitol, various hexitols, dulcitol,pentaerythritol, sorbitan, mannitan, dipentaerythritol monoether, andother similar compounds. Such particular types in which higherhydroxylated materials are Isubjected to oxyalkylation and then employedin the same manner as oxyalkylated glycerol, is employed in the presentinstance, are not contemplated in this specific case, although attentionis directed to the same.

Reference is also made to other oxyalkylated compounds which may be usedas reactants to replace oxyalkylated glycerol, or oxyalkylated ethyleneglycol, which latter reactant is described in a co-pending applicationhereinafter referred to. The reactants thus contemplated include thepounds, but since, for all practical purposes, they can be so indicated,and since such practice is common in the arts concerned with materialsof.

this type, it isso adopted here. Thus, reieren e hydroxyl groups. Forinstance, the oxyalmlated derivatives, particularly the oxyethylatedderivatives of ethyldiethanolamine, bis(hydroxyethy1) acetamide, theacetamide of tris(hydroxymethyhaminomethane, tetrahydroxylated ethylenediamine, etc. Compounds may also be derived from cyclic diglyicerol andthe like. Furthermore, for convenience, attention is directed to asomewhat similar class of materials which are described in U. 8. PatentNo. 2,296,600, dated September 8, 1942, to De Groote and Keiser. Saidpatent involves the use of the same type of alcoholic bodies forreactants, but is limited, among other things, to the compounds whichare essentially symmetrical in nature, for instance, involving theintroduction of two alcoholic residues, whereas, in the presentinstance, one, two, or three, or more, might he introduced. As indicatedpreviously, the polybasic acids employed are limited to the type havingnot more than eight carbon atoms, for example, oxalic, malonic,suocinic, glutaric, adipic, maleic, and iphthalic. Similarly, one mayemploy acids such as fumaric, glutaconic, and various others, such ascitric, malic, tartaric, and the like. The selection of the'particulartribasic or dibasic acid employed, is usually concerned largely with theconvenience of manufacture of the finished ester, and also the price ofthe reactants. Generally speag, phthalic acid or anhydride tends toproduce resinous materials, and greater care must be employed if theultimate or final product be of a sub-resinous type. Specifically, thepreterred type of polybasic acid is such as to contain six carbon atomsor less. Generally speaking, the higher the temperature employed, theeasier it is to obtain large yields of esteriiied product, althoughpolymerization may be stimula. Oxalic acid may be comparatively cheap,but it decomposes readily at slightly above the boilin point of water.For this reason it is more desirable to use an acid which is moreresistant to pyrolysis. Similarly. when a, poly basic acid is availablein the form oi an anhydride, such anhydride is apt to produce the esterwith greater case than the acid itself. For this reason, maleicanhydride is particularly adaptable, and also, everything elseconsidered, the cost is comparatively low on a per molar basis, eventhough somewhat higher on a per pound basis. Succinic acid or theanhydride has many attractive qualities oi maleic anhydride, and this isalso true of adipic acid. For purposes of brevity, the bulk of theexamples, hereinafter illustrated, will refer to the use of maleicanhydride, although it is understood that any other suitable polybasicacid may be employed. Furthermore, reference is made to derivativesobtained by oxyethylation. although, as previously pointed out, otheroxyalkylating agents may be employed.

As far as the range of oxyethylated glycerols employed as'reactants isconcerned, it is our preference to employ those in which approximatelyto 24 oxyethylene groups have-been introduced into. a single glycerolmolecule. .This means that approximately five to eight oxyethyleneradicals have been introduced for each original hydroxyl group.

The oxyalkylation of glycerol is a well known procedure (see Example 11of German Patent No. 605,973, dated November 22, 1934, to I. G.Parthenindustrie Akt. Ges). The procedure indicated in the followingthree examples is substantially identical with that outlined in saidaforementioned German patent.

all

Oxrrrmmrsn Governor.

Example 1 184 pounds of glycerol is mixed with Vz%. by weight, ofcaustic soda solution having a specific gravity or 1.383. The causticsoda acts as a catalyst. The ethylene oxide is added in relatively smallamounts, for instance, about it pounds at a time. The temperatureemployed is from ISO-180 C. Generally speaking, the gauge pressureduring the operation approximates 200 pounds at the maximum, and whenreaction is completed, drops to zero, due to complete absorption of theethylene oxide. When all the ethylene oxide has been absorbed and thereactants cooled, a second portion, for instance, as more pounds ofethylene oxide, are added and the procedure repeated until the desiredratio oi 15 pound moles of ethylene oxide to one pound mole of glycerolis obtained. This represents 660 pounds of ethylene oxide for 92 poundsof glycerol.

Oxvx'rnxm'rsn GLYCEROL Example 2 The ratio of ethylene oxide isincreased to 18 pound moles for each pound mole of glycerol. Otherwise,the same procedure is followed as in Example 1, preceding.

OxYErrrvLA'rEo GLYCEROL Example 3 The same procedure is followed as inthe two previous examples, except that the ratio of ethylene oxide toglycerol is increased to 21 to one.

Oxrxrrrrmrxo GLYcsRoL Manners Example 1 One pound mole of oxyethylatedglycerol (l to 15 ratio) prepared in the manner previously described istreated with one pound mole of maleic anhydride and heated atapproximately C. for approximately thirty minutes to two hours, withconstant stirring, so as to yield a monomaleate.

Oxvnrnrmrro GLYcsnor. MALEATE Example 2 The same procedure is followedas in the preceding example, except that two moles of maleic anhydrideare employed so as to obtain the dimaleate instead of the monornaleate.

Oxvs'ra' zns'rxc Gtxcsxor. Mates-rs Example 3 The same procedure isfollowed as in the two preceding examples, except that three moles ofmaleic anhydride are employed so as to obtain the trimaleate.

OxYsrr-rrm'rsn GLYCEROL MALEATE Example 4 The same procedure is employedas in the preceding examples, except that oxyethylated glycerol (ratio 1to 18) is substituted in place of oxyethylated glycerol (ratio 1 to 15).

OxYsrnYLA'rEn GLYcsRoL Marmara Example 5 The same procedure is employedas in the preceding examples, except that oxyethylated glycerol (ratio 1to 21) is employed instead of oxyethylated glycerol (ratio 1 to 15) or(i to 18).

Previous reference has been made to an alcoholic body which has beendefined generically by the formula R1(OH) m. The sub-generic class ofalcoholic compounds employed as reactants in the manufacture of thepresent compounds, are

combine with alkalies such as caustic soda, caustic potash, ammonia,triethanolamine, and the like, to produce soap or soap-like materials.The best examples are, of course, the higher fatty acids, such as oleicacid, stearic acid, palmitic acid, etc. In addition to the higher fattyacids, other well knownmembers of this class include resinic acids,abietic acids, naphthenic acids, and acids obtained by the oxidation ofpetroleum hydrocarbons and commonly referred to as oxidized wax acids.

Generally speaking, the higher fatty acids are apt to contain from 12-14carbon atoms as a lower limit, to 18-22 carbon atoms as an upper limit.Oxidized wax acids may contain as many as 32 carbon atoms.

It is well known, of course, that amides may be obtained by reactionbetween long chain carboxy acids and monoalkylolamines, such asmonoethanolamine, monopropanolamine, monobutanolamine, etc. Themanufacture of such chemical compounds, particularly where derived fromhigher fatty acids, is described in British Patent No.'450,672, datedJuly 17, 1936, to Orelup. An-

other procedure which has been employed for the same purpose is to reactthe monoalkylolamine with the acyl chloride derived from a suitablecarboxy acid. Still another method employs the use of an alkylene oxide,such as ethylene oxide, propylene oxide, butylene oxide, and the like,in

connection with an amide. Reference is made to U. S. Patent No.2,002,613, dated May 28, 1935, to Orthner and Keppler. This lattermethod for producing oxyamides is not limited to the use ofalkylolamines, such as monoalkylolamines, dialkylolamines, or the like,as the raw material, but may employ alkylolamines, arylamines,aralkylamines, alicyclic amines, etc., so as to obtain hydroxylatedderivatives. Naturally, the methods employing monoalkylamines, andparticularly the process in which acyl chloridesare employed, may alsouse such materials as diethanolamine, dipropanolamine, dibutanolamine,and the like. Amides so obtained may have as many as six hydroxylradicals in the aminohydrogen position.

It is known, of course, that when primary and secondary amines arereacted with various alkylene oxides, one may obtain hydroxyethylalkylamines, hydroxypropyl alkylamines, etc. The reaction, for example,between a primary amine and ethylene oxide, yields a material of theformula type HO.CH:i.CHz.NI-IR. Such amines may be reacted withdetergent-forming carboxy acids to give suitable amides. I

Briefly, then, in a practical way amides can be derived fromdetergent-forming acids or some derivative, usually an ester.Ihdeed,'esters are often more suitable reactants for amidification thanthe acids themselves. As to the manufacture of esters, see the followingUnited States patents, to wit: No. 1,160,595, dated Nov. 16, 1915, toGruter et al.; No. 2,221,674, dated Nov. 12, 1940, to Ellis; and No.2,177,407, dated Oct. 24, 1939, to Hansley. See also Organic syntheses,volume X, page 88, 1930. 4

As to the procedure for the manufacture of amides or substituted amides,see the following United States patents: No. 2,058,013, dated Oct. 20,1936, to Henke et al.;-N0. 2,013,108, dated Sept. 3, 1935, to Reppe etal.; No. 1,475,477, dated Nov. 27, 1923, to Ellis; and No. 1,954,433,dated Apr. 10, 1934, to Thomas et al.

In any event, suitable amides having been obtained, either from theacids, esters, or any other derivatives, they may then be treated withethylene oxide, propylene oxide, butylene oxide, glycid, or the like.Similarly, instead of obtaining the amides, one may obtain thesubstituted amides, i. e., the derivatives of amylamine,cyclohexylamine, aniline, benzylamine, or the like, particularly thesubstituted amides, in which the hydrocarbon radical replacing an aminohydrogen atom contains not over 7 carbon atoms. Such substituted amidesthen can be treated with oxyalkylating agents in the same mannerpreviously described in connection with the amides.

Another suitable procedure is simply to react the selected ester or acidor other suitable derivative, with a hydroxylated primary amine, such asmonoethanolamine, monopropanolamine, monobutanolamine,monoglycerylamine, tris (hydroxymethyl)aminomethane, and the like. Suchreactants readily yield the hydroxylated amide of the kind contemplated.

Reactions can also be conducted with secondary hydroxylated amines ofthe kind exemplifled by diethanolamine, diproponolaxnine,diglycerylamine, etc. When this latter type of reactants is employed,one is more apt to obtain a significant amount of esterified compoundalong with the amide derivative. The same also applies when material ofthe type exemplified by ethyl ethanolamine, phenyl ethanolamine,cyclohexyl ethanolamine, etc.,

are employed for amidification. In any event,

one can readily obtain amides of the kind in dicated by the followingformulas, in which RC0 is the acyl radical of a detergent-forming acid:

H BCON/ 0.11.011 n RCON/ ac ON 0,1140 02117003114011 where D is ahydrocarbon radical.

H RCON/ on Call! on where D is a hydrocarbon radical.

RCON onion c-cruon =cnion Our preferred amides are derivatives of fattyC2H4OH RC ON CIHAOH RC'ON 0H CaHs acids and especially unsaturated fattyacids, such as oleic acid, ricinoleic acid, etc.

COMPLETED Monomers Derrvsrrvr:

Eotample 1 One pound mole of a product of the kind described under theheading Oxyethylated glycerol maleate, Example 1" is reacted with onepound mole of hydroxyethyloleoamide, preferably in the absence of anyhigh boiling hydrocarbon or inert solvent. However, if an inertvaporizing solvent is employed, it is generally necessary to use onewhich has a higher boiling range than xylene, and sometimes removal ofsuch solvent might present a dimculty. In other instances, however, suchhigh boiling inert vaporizing solvent, if employed, might be permittedto remain in the reacted mass and appear as a constituent or ingredientof the final product. In any event, our preference is to conduct thereaction in the absence of any such solvent and permit the reaction toproceed with the elimination of water. The temperature of reaction isabout 180 to200 C. and time of reaction about 20 hours.

COMPLETED Monosrenrc DERIVATIVE Example 2 The same procedure is followedas in Completed monomeric derivative, Example 1, preceding, except thatthe dimaleate described under the heading Oxyethylated g ycerol maleate,Example 2 is used instead of the monomaleate.

COMPLETED Morrommuc Dsnrvarrvn Example 3 The same procedure is followedas in the two preceding examples, except that the trimaleate issubstituted for the monomaleate or dirnaleate in the two precedingexamples.

Commerce MoNomEiuc DERIVATIVE Example 4 The same procedure is followedas in Examples 2 and 3, immediately preceding, except that for eachpound mole of the dimaleate, or each pound mole of the trimaleate,instead of using one pound mole of hydroxyethyl oleoamide as a reactant,one employs two pound moles. I

COMPLETED Monomuuc Dnnrvorrvr:

Example 5 The same procedure is followed as in Example 3, preceding,except that for each pound mole of trimaleate, instead of adding onepound mole of hydroxyethyl oleoamide, one adds three pound moles ofhydroxyethyl oleoamide, for reaction.

COMPLETED MONOMERIC DERIVATIVE Example 6 Comte-run Monorrearc DsnrvarrveExample 7 COMPLETED MoNomEnIc DsluvArrvn Example 8 The same procedure isfollowed as in Examples l to 7, preceding, except that bis(hy--droxyethyl)oleoalmide is substituted for hydroxyethyl olcoamide.

Compress MONOMERIC Dcsrvo'rrva Example 9 The same procedure is followed,as in Examples l to 'l, preceding, except that hydroxyethylricinoleoamide is substituted for hyroxyethyl oleoamide.

Comrrsrsn Monorssnrc Dsnrvsrrvs Example 10 The same procedure isfollowed as in Examples 1 to 7, preceding, except that bis(hydroxyethyl)ricinoleoamide is substituted for hydroxyethyi oleoamide.

The method of producing such fractional esters is well Mom The generalprocedure is to employ a. temperature above the boiling point of waterand below the pyrolytic point of the reactants. The products are mixedand stirred constantly during the heating and esteriflcation step. Ifdesired, an inert gas, such as dried nitrogenor dried carbon dioxide,may be passed through the mixture. Sometimes it is desirable to add anesteriflcation catalyst, such as sulfuric acid, benzene sulfonic acid,or the like. This is the same general procedure as employed in themanufacture of ethylene glycol dihydrogen diphthalate. (See U. 8. PatentNo. 2,075,107, dated March 30, 1937, to Frasier.)

Sometimes esterification is conducted most readily in the presence of aninert solvent, that carries away the water of esterlfication which maybe formed, although as is readily appreciated. such water ofesteriflcation is absent when such type of reaction involves an acidanhydride, such as maleic anhydride, and a glycol. However, if water isformed. for instance, when citric acid is employed, then a. solvent suchas'xylene may be present and employed to carry off the water formed. Themixture of xylene vapors and water vapors can be condensed so that thewater is separated. The xylene is then returned to the reaction vesselfor further circulation. This is a conventional and well-known procedureand requires no further elaboration.

In the previous monomeric examples there is a definite tendency, inspite of precautions. at least in a number of instances, to obtainpolymeric ma.- terials and certain cogeneric by-products. This istypical, of course, of organic reactions of this kind, and as iswellknown, organic reactions per so are characterized by the fact thatyields are the exception, rather than the rule, and that significantyields are satisfactory, especially in those instances where thelay-products or cogeners may satisfactorily serve with the same purposeas the principal or intentional product.

This is true in the present instance. In many cases when the compound ismanufactured for purposes of demulsification, one is better off toobtain a polymer in the sense previously described, particularly apolymer whose molecular weight is a rather small multiple of themolecular weight of the monomer, for instance, a polymerwhose molecularweight is two, three, four, five, or six times the molecular weight ofthe monomer. Polymerization is hastened by the presence of an alkali,and thus, in instances where it is necessary to have a maximum yield ofthe monomer, it may be necessary to take such precautions that thealkali used in promoting oxyethylation oi" glycerol, be removed beforesubsequent reaction. This, of course, can be done in any simple mannerby conversion to sodium chloride, sodium sulfate, or any suitableprocedure.

In the preceding examples of the Completed monomeric derivative,Examples 1 to 10, inclusive, no reference is made to the elimination ofsuch alkaline catalyst, in view of the effectiveness of the low multiplepolymers as demulsifiers. Previous reference has been made to the factthat the carboxylic hydrogen atom might be variously replaced bysubstituents including organic, radicals, for instance, the radicalsobtained from alcohols, hydroxylated amines, non-hydroxylated amines,polyhydric alcohols, etc. Obviously, the reference is also true, in thata free hydroxyl group may be esterified with a. selected acid, Varyingfrom such materials as ricinoleic acid to oleic acid, including alcoholacids, such as hydroxy acetic acid, lactic acid,-ricinoleic acid andalso polybasie. acids of the kind herein contemplated.

With the above facts in mind, it becomes obvious that what has beenpreviously said as to polymerization, with the suggestion that byproducts or cogeneric materials were formed, may be 1 recapitulatedwith. greater definiteness, and one can readily appreciate that theformation of heatrearranged derivatives or compounds must take place toa greater or lesser degree. Thus, the products 'herein contemplated maybe characterized by being monomers of the type previously described, oresterification polymers, or the-heatrearranged derivatives of the same,and thus including the heat-rearranged derivatives of both the polymersand esterification monomers, separately and Jointly. Although the classof materials specifically contemplated in this instance is acomparatively small and narrow class of a broad genus, yet it isobviously impossible to present any adequate formula which wouldcontemplate the present series in their complete ramification, except ina manner employed in the hereto appended claims.

Although the products herein contemplated vary so broadly in theircharacteristics, i. e., monomers through sub-resinous polymers, solubleproducts, water-emulsifiable oils or compounds, hydiotropic materials,balsams, sub-resinous materials, semi-resinous materials, and the like,yet there is always present the characteristic unitary hydrophilestructure related back to the oxyalkylation, particularly. theoxyethylation of the glycerol used as the raw material. As hereinafterindicated, in practising our process, the demulsifier may be added tothe emulsion at the ratioof 1 part in 10,000, 1 part in 20,000, 1 partin 30,000, or for that matter, 1 part in 40,000. In such ratios it wellmay be that one cannot diflerentiate between the solubility of acompound completely soluble in water in any ratio, and a semiresinousproduct apparently insoluble in water in ratios by which ordinaryinsoluble materials are characterized. However, at such ratios theimportance must reside in interfacial position and through the entireseries, notwithstanding variation in molecular size and physicalmake-up, isv

absolutely apparent. Such statement is an obvious'oversimplification ofthe rationale underlying demulsification, anddoes not even consider theresistance of an interfacial film to crumbling,

displacement, being forced into solution, altered wetability and thelike. As to amidiiication polymers, for instance, where Z is apolyaminoamide radical, see what is said subsequently.

COMPLETED POLYMERIC DERIVATIVES INCLUDING HEAT-REARRANGED COGENERSExample 1 COMPLETED POLYMERIC DERIVATIVES INCLUDING HEAT-REARRANGED-CocsNaRs Example 2 The same procedure is followed as in the precedingexample, except that polymerization is continued, using either asomewhat longer reaction time, or it may be, a somewhat highertemperature, or both, so as to obtain a material having a molecularweight of approximately three to four times that of the initial product.

COMPLETED POLYMERIC DERIVATIVES INCLUDING HEAT-REARRANGED CocENnasExample 3 The same procedure is followed as in Examples 1 and 2,preceding, except that one employs as reactants amides derived fromtris(hydroxymethyDaminomethane, instead of amides of diethanolamine.

COMPLETED POLYMERIC DERIVATIVES INCLUDING ,HEAT-REARRANGBD COGENERS E:rample 4 The same procedure is followed as in Examples 1 to 3,preceding, except that one polymerizes a mixture instead of a singlemonomer, for instance, a mixture of materials of the kind described inCompleted monomeric derivative, Example 3, and in Completed'monomericderivative, Example 4,.are mixed in molecular proportion and subjectedto polymerization in the manner indicated in the previous examples.

It is understood, of course, that the polymerized product need not beobtained as a result of a twostep procedure. Inother words, one need notconvert the reactants into the monomer and then subsequently convert themonomer into the polymer. The reactants may be converted through themonomer to 'the polymer in one step. Indeed, the formation of themonomer and polymerization may take place simultaneously. This isespecially true if polymerization is conducted astaeea in the absence ofan inert solvent, as previously described, and if one uses acomparatively higher temperature, for instance, approximately 220 C. forpolymerization. Thus, one pound mole of oxyethylated glycerol maleate ofthe kind described, ratio 1 to 15, up to l to 21, is mixed with twomoles of hydroxyethyl ricinoleoamide and reacted for 30 hours atapproximately 220 0., until the mass is homogeneous. It is stirredconstantly during reaction. Polyfunctionality may reside in dehydration(etherization) of two hydroxyl groups attached to dissimilar molecules.

The fact that the polymerized and heat-rearranged products can be madein a single step, illustrates a phenomenon which sometimes occurs eitherin such instances where alcoholic bodies 4 the reagent or demulsifyingagent contemplated of the kind herein illustrated arecontempiated asreactants, or where somewhat kindred alcoholic bodies are employed. Thereactants may be mixed mechanically to give a homogeneous mixture, or ifthe reactant do not mix to give a homogeneous mixture, then early in thereaction stage there is formed, to a greater or lesser degree,sufllcient monomeric materials so that a homogeneous system is present.Subsequently, as reaction continues, the ystem may become heterogeneousand exist in two distinct phases, one being possibly an oily body ofmoderate viscosity, and the other being a heavier material, which issticky or sub-resinous in nature. In many instances it will be foundthat the thinner liquid material is a monomer and the more viscous orresinous material is a ploymer, as previously described. Such productcan be used for demulsiflcation by adding a solvent which will mutuallydissolve the two materials, or else, by separating the two heterogeneousphases and employing each such as water; petroleum hydrocarbons such asgasoline, kerosene, stove oil, a coal tar product such as benzene,toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols,particularly in our herein described process for breaking petroleumemulsions, is based upon its ability to treat certain emulsions moreadvantageously and at a somewhat lower cost than is possible with otheravailable demulsiflers, or conventional mixtures thereof. It is believedthat the particular demulsii'ying agent or treating agent hereindescribed will find comparatively limited application, so far as themajority of oil field emulsions are concerned; but we have found thatsuch a demulsifying agent has commercial value, as it will economicallybreak or resolve oil field emulsions in a number of cases which cannotbe treated as easily or at so low a cost with the demulsiiylng agentsheretofore available.

In practising our improved process for resolving petroleum emulsions ofthe water-in-oil type, a treating agent or demulsifying agent of thekind above described is brought into contact with or caused to act uponthe emulsion to be treated, in any of the various ways, or by any of thevarious apparatus now generally used to resolve or break petroleumemulsions with a chemical reagent, the above procedure being used eitheralone, or in combination with other demulsifying procedure, such as theelectrical dehydration process.

The demulsifler herein contemplated may be employed in connection withwhat is commonly known as down-the-hole procedure, 1. e., bringing thedemulsifier in contact with the fluids of the well at the bottom of thewell, or at some point prior to their emergence. This particular type ofapplication is decidedly feasible when the demulslfler is used inconnection with acidification of calcareous oil-bearing strata,especially if suspended in or dissolved in the acid employed foracidification.

cognizance must be taken of the fact that the surface of the reactingvessel may increase or aliphatic alcohols, such as methyl alcohol, ethylalcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexylalcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneoussolvents, such as pine oil, carbon tetrachloride, sulfur dioxide,extract obtained in the refining of petroleum, etc., may be employed asdiluents. Similarly, the material or materials herein described, may beadmixed with.one or more of the solvents customarily used in connectionwith conventional demulsifying agents, provided that such compounds arecompatible. They will be compatible with the hydrophile type of solventin all instances, Moreover, said material or materials may be usedalone, or in admixture with other suitable well known classes 0!demulsifying agents.

It is well known that conventional demulsifysignificant, because saidreagents undoubtedly have solubility within the concentration em-I-Iowever, since such re-' decrease reaction rate and degree ofpolymerization, for instance, an iron reaction vessel speeds up reactionand polymerization, compared with a glass-lined vessel.

As has been previously indicated, the sub-genus employed as an alcoholin the present instance is one of a series of alcoholic compounds whichare contemplated in our oo-pending applications Serial Nos. 447,151;447,152; 447,153; 447,154: 447,-

ployed. same fact is true in regard to the 167 and 447,168, filed June15. 1942.

Having thus described our invention, what we claim as new and desire tosecure by LettersPateat is:

1. A process for breaking petroleum emulsions or the water-in-oil type.characterized by subjecting the emulsion to the action of a demulsiilercomprising a member of the class consisting of monomers, sub-resinousesteriflcation polymers, and cogenerlc sub-resinous heat-rearrangedderivatives oi the monomers and aforementioned polymers, separately andJointly, and of the following formula:

' arol-ammon a],

(C.H|..0)- 0OCR in which R is the carboxyl-i'ree radical or apolynumerals to 2; 11 represents the numerals 0 to 2;

2 represents the numerals 1 to 3; 2: represents the polymers, separatelyand jointly, and of the following formula:

numerals 0 to l; and 1! represents the numerals 2. A process forbreaking petroleum emulsionsof the water-in-oil type, characterized bysubjecting the ernulsion to the action of a demulsifier comprising amember of the class consisting of monomers, sub-resinous esteriflcationpolymers, and cogeneric sub-resinous heat-rearranged derivatives of themonomers and aforementioned polymers, separately and jointly, and of thefollowing formula:

'[(c,.Hi..0),.'0ocR000z],

CaH503-[(C1|H2no)n'H]v [(C,.Hh0)..'00CRCO0R in which R is acarboxyl-free radical of a dibasic carboxy acid having not over 6 carbonatoms; R1 is a water-insoluble detergent-forming acid amide radical, inwhich the acyl radical contains more than 8 carbon atoms and not morethan 32.carbon atoms and in which at least one amido hydrogen atom hasbeen replaced by a hydroxy hydrocarbon radical; Z is an acidic hydrogenatom equivalent including the acidic hydrogen atom itself; n representsthe numerals 2 to 4; n represents the numerals 3 to 10; :2: representsthe numerals 0 to 2; 11 represents the numerals 0 to 2;

and e represents the numerals 1 to 3.

3. A process for breaking petroleum emulsions of the water-in-oil type,characterized by subjecting the emulsion to the action of a demulsifiercomprising a member of the class consisting of monomers, sub-resinousesteriflcation polymers, and cogeneric sub-resinous heat-rearrangedderivatives of the monomers and aforementioned polymers, separately andjointly. and of the following formula:

' [(C2H40)1|'OOCRCOOZ]= C3H:O8' 2H4O)n' ]ir llcznlowoocncooml. in whichR is a carboxyl-free radical of a dibasic carboxy acid having not over 6carbon atoms; R1 is awater-insoluble detergent forming acid amideradical, in which the acyl radical contains more than 8 carbon atoms andnot more than 32 car bon atoms and in which at least one amido hydrogenatom has been replaced by a hydroxy hydrocarbon radical; Z is an acidichydrogen atom equivalent including the acidic hydrogen atom itself; itrepresents the numerals 3 to 10; a: represents the numerals 0 to 2; 11represents the nuznearals 0 to 2; and 2: represents the numerals l 4. Aprocess for breaking petroleum emulsions oi the water-in-oil type,characterized by subjecting the emulsion to the action of a demulsifiercomprising a polar member of the class consist ing of monomers,sub-resinous esterifica'tion polymers, and cogeneric sub-resinousheat-rearranged derivatives of the monomers and aforementioned i5 inwhich R is a carbonyl-free radical of a dibasic carboxy acid having notover 6 carbon atoms; R1

is a water-insoluble detergent-forming acid amide radical, in which theacyl radical contains more than 8 carbon atoms and not more than 32carbon atoms and in which at least one amido hydrogen atom has beenreplaced by a hydroxy hydrocarbon radical; Z is" an acidic hydrogen atomequivalent including the acidic hydrogen atom itself; 12. represents thenumerals 3 to 10; 0: represents the numerals 01:0 2; y representsthenumerals 0 to 2; and 2 represents the numerals l to 3.

5. A process for breaking petroleum emulsions of the water-in-oil type,characterized by subjecting the emulsion to the action of a demulsifiercomprising a polar acidic member of the class consisting of monomers,sub-resinous esterification polymers, and cogeneric sub-resinousheat-rearranged derivatives of the monomers and aforementioned polymers,separately and jointly, and of the following formula:

in which R. is a carboxyl-free radical of a dibasic carboxy acid havingnot over 6 carbon atoms; R1 is a water-insoluble detergent-forming acidamide radical, in which the acyl radical contains more than 8 carbonatoms and not more than 32' carbon atoms and in which at least one amidohydrogen atom has been replaced by a hydroxy hydrocarbon radical; Z isan acidic hydrogen atom equivalent including the acidic hydrogen atomitself; n represents the numerals 3 to 10; :1: represents the numerals 0to 2; y represents the numerals 0 to 2; and 2 represents the numerals lto 3. v

6. A process for breaking petroleum emulsions of the water-in-oil type,characterized by subjecting the emulsion to the action of a demulsifiercomprising a polar acidic member of the class consistingv of monomers,sub-resinous esteriflcation polymers, and cogeneric sub-resinousheatrearranged derivatives of the monomers and aforementioned polymers,separately and jointly, and of the following iormula:

in which R is a carboxyl-free radical of a dibasic carboxy acid havingnot over 6 carbon atoms; R1 is a higher fatty acid amide radical, inwhich the acyl radical contains more than 8 carbon atoms and not morethan 32 carbon atoms and in which at least one amido hydrogen atom hasbeen replaced by a hydroxy hydrocarbon radical; Z is an acidic hydrogenatom equivalent including the acidic hydrogen atomv itself; 11'represents the numerals v3 to 10; :1: represents the numerals 0 to 2; 11represents the numerals 0 to 2; and z repre sents the numerals 1 to 3.

'7. A process for breaking petroleum emulsions of the water-in-oil type,characterized by subiect-- ing the emulsion to the action of ademulsifier comprising a polar acidic member 'of the consisting ofmonomers, sub-resinous esterification polymers, and cogenericsub-resinous heatrearranged derivatives of the monomers andaforementioned polymers, separately and jointly, and of the followingformula:

in which R is a carboxyl-free radical of a dibasic carboxy acid havingnot over 6 carton atoms; R1 is an unsaturated higher fatty acid amideradical, in which the acyl radical contains more than 8 carbon atoms andnot more than 32 carbon atoms and in which at least one amido hydrogenatom has been replaced by a hydroxy hydrocarbon radical; Z is an acidichydrogen atom equivalent including the acidic hydrogen atom itself; 11.represents the numerals 3 to 10; m represents the numerals 0 to 2; 1/represents the numerals 0 to 2; and 2 represents the numerals 1 to 3.

8. A process for breaking petroleum emulsions of the water-in-oil type,characterized by subjecting the emulsion to the action of a demulsifiercomprising a polar acidic member of the class consisting of monomers,sub-resinous esterification polymers, and cogeneric sub-resinousheatrearranged derivatives of the monomers and aforementioned polymers,separately and jointly, and of the following formula:

in which R is acarboxyl-free radical of a dl'nasic carboxy acid havingnot over 6 carbon atoms; R1 is a substituted ricinolecamide in which atleast one amido hydrogen atom has been replaced by a hydroxy hydrocarbonradical; Z is an acidic hydrogen atom equivalent including the acidichydrogen atom itself; 11' represents the numerals 3 to 10; :1:represents the numerals 0 to 2; 3/ represents the numerals 0 to 2; and 2represents the numerals 1 to 3.

MELVIN DE GROOTE.

BERNHARD KEISER.

